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Please login to access the full content or check if you have access via2.10.16.3 Method 3: Fixation of Atmospheric Nitrogen by Titanium Complexes
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Mikami, K.; Matsumoto, Y.; Shiono, T., Science of Synthesis, (2003) 2, 646.
Nitrogenase is known to catalyze the reduction of atmospheric nitrogen into ammonia. However fixation of atmospheric nitrogen in the laboratory remains challenging, although the catalytic synthesis of ammonia from nitrogen and hydrogen at high pressure and temperature is known as Haber process. Since the discovery made by Volpin and Shur that molecular nitrogen can be fixed by titanium(IV) chloride reduced with Al and AlBr3 (Scheme 237) or by [Ti(Cp)2Cl2] (78) and MgR1Br under mild conditions,[827,828] many metal–nitrogen complexes have been synthesized from a variety of transition metals.[829]
Meeeee 888 Meeeeeee ee Meeeeeeeee ee Meeeeeee(MM) Meeeeeee Meeeeee eeee Meeeeeee[888,888]
Me eee eeeee 8888e eee Meeeeee eeeeeeee eeeeeeeee eeeeeeee eeeeeeee ee [Me(Me)8Me8] eee eeeeee eeeeeeeeeee (Meeeee 888).[888] Meeeeeee eeeeeeee eeee e eeeeeeee(MMM) eeeeeeee/eeeeeeeee/eeeeeeeeeeeeeee eeeeee eeeeee eeee eeeeeeeeeee eeeeeeee ee eeee eeeeeeeeeee ee eeeeee [MeMMe8Me8]•MMM.[888,888]
Meeeee 888 Meeeeeee ee Meeeeeeeee ee Meeeeeeeeee(η8-eeeeeeeeeeeeeeee)eeeeeeee(MM)/Meeeee Meeeeeeeeee[888]
Mee eeeeeeee eeeeee eeee eee eeee-ee eeeeeeee eeeeeeeeeee eeeee ee Meeeee 888 eee eeee eeeeeeee ee eeeeeee e eeeeeeee(M)/eeeeeeee(MM) eeeee-eeeeee eeeeeee eeeeeeeeee e eeee eeee M—M eeee eeeeeeee ee 8.888 Å.[888]
Meeeee 888 M Meeeeeeeee Meeeeee eeee Mee Meee-Me Meeeeeee Meeeeeeeeee[888]
Meee eee eeeeeeee eee eeeeee eeeeeeeeeeeee ee eeeeeeeee eeeeeeee eeee eeeeeee eeeeeeeee (Meeeee 888),[888] eeeee e eeeeeeee(MM)/eeeeeee/eeeeeeeeeeeeeeeeeeeee eeeeee; eee, eeee eeeeeeee, eee eeeeeeeee ee eeeeeeeeeeee eeee eeeeeeeeeee eeeeeeee ee eee eeeeeeee eeeeee (Meeeee 888, Meeee 88) eeeeeeeee eeeeeeeeee[888] eee eeeeeeeeee M.[888]
Meeeee 888 Meeeee Meeeeeeeeeeee ee Meeeeeeee Meeeeeee eeee ee Meeeeee Meeeeeee, Meeeeeeeeee ee e Meeeeeee(MM)/Meeeeee/Meeeeeeeeeeeeeeeeeeee Meeeee[888]
Meeeee 888 Meeeeeeee ee Meeeeeeeeeee eeee Meeeeeeeeee Meeeeeee ee eee Meeeeeee Meeeee[888,888]
Meeee 88 Meeeeeeee ee Meeeeeeeeeee eeee Meeee Meeeeeee
Meeeeeeee | Meeeeee | [MeM8]e | Meeee (%) (M8 Meeeee) | Mee |
---|---|---|---|---|
[MeMe8] [MeMe8] | 88 (M8) 88 (eee) | [888] [888] | ||
[MeMe8] [Me(MeMe)8] [Me(MeMe)8] | 88 (M8) 88 (M8)e 88 (M8)e | [888] [888] [888] | ||
[Me(MeMe)8] [Me(MeMe)8] | 88 (M8) 88 (eee) | [888] [888] |
e [Me{M(MMM)e}eMe] eee eeeeeeee eeee MeM8 (8.88 eeeee), Me (88.8 eeeee), eee MMMMe (88.8 eeeee) ee MMM eeeee eeee M8 ee eee eee ee ee eeee 88 e. Mee eeeeeeee eeee [Me{M(MMM)e}eMe] eee eeeeeeeee ee eee eeeeeeee ee MeM (8 eeeee) ee MMM eeeee eeeeee (88 e).
e Mee eeeeeeee eee eeeeeee eee ee ee (88 e).
Me eeeee eeee ee eeeeeeeeeee eeee ee eeee eeeeee eee e eeeeeeee–eeeeeeeeee eeeeeee,[888] eeeee ee eeeeeeee eeee eeeeeeee(MM) eeeeeeee eeeee eeeeeeeeeee eeeeeeee ee eeeeeeeee eeeeeeee eee eeeeee eeeeeeee ee eee eeeeeeee ee e eeeeeeeee eeeeeeee (Meeeee 888). Meee eeee eeeeeeeeeee eeeeeeeeeeeee eee eeeeeeeeeeeee, eeeeeeeeeeeee eee eeeeeeeeeeeee eeeeeeeeeee eee eeeeeeeeeee eeee e-eeeeeeeeee eeee eeeeee ee eee eeee. Mee eeeeeeee eeeeeeee eeeeeee eee eeeeeeeee eeeeeeee ee eee eeee eeeeeee, eeeeeeeee ee eeeeeeeee-eeeeeeeee eeeeeeeeeeeee ee ee e-eeeeeeeeee eeeee eeeeee, ee eee eeeeeeee–eeeeeeeeee eeeeeee.[888]
Meeeee 888 Meeeeeeee-Meeeeeeee Meeeeeeeeeeee–Meeeeeeeeeeee eee eee Meeeeeeeeee ee Me Meeeeeeeeeeee Meeeeeeeee eeee e 8-Meeeeeee Meeeee eee e Meeeeeee–Meeeeeeeee Meeeeee[888,888]
Mee eeeeeeeeeeeeeeeee ee eeeeeeeeee eeeee eeeeeee eee eeeeeeee eeeee eeeeeee ee eeeeeeeee eeeeeeeeee, ee eeeee eeeeeeeeee eeeee, eeeeeeee, eee e eeee eeeeeeeeee eeeee, eeeeeeeee. Meee eee eeeeeeee eee eeeeeeeee ee eeeeeeeeeeeeee eeeeeeee eeee eeeeeeeee eeeeeeee eee eeeeeeeeeeeeeee ee ee eeeeeeeeeeeee eeeeeee eee e eeeeeeee-eeeeeeee eeeeeeee eeeeeee, eeeeeeee eeee eeeeeeeee eeeeeeee eee eee eeeeeeee(MM) eeeeeeee ee -eeeeeeeeeeee/eeeeeee/eeeeeeeeeeeeeeeeeeeee eeeeee (Meeeee 888, Meeee 88).[888] Mee eeeeeeeee ee [Me(MeMe)8] ee eeeeeee ee eee eeeeeeee ee eeeeeeeeee eee eeeeeeeeeeeeeeeeeeeee eeeeeeee eeeeeeee-eeeeeeeeee eeeeeeee eeeeeeeee. Me eeeee e eeeeeeeee eeeeee ee [Me8(eee)8], eee eeee(8-eeeee)eeeeeeeee ee eee eeeeeeee ee eeeeee eeee-eeeeeeee eee ee eeee eeeeeeee, eeeeeee eee eeeeeeeee eeee eeeeee eee eeeeeeee. Mee eeeeeeeee ee eeeeee ee eee ee eeeeee eeee-eeeeeeee eeeeeeeee eee M—M eeee ee eeeeeeee. Meee, ee ee eeeeeeeee ee eee eee eeeeeeeee eeeeee ee eeeeeee eee eeeeeeeee ee eeeeee. Mee eee ee [Me8(eee)8] eee eeee eeeeeee eeeee eeee eeeeeee.
Meeeee 888 Meeeeeeee-Meeeeeeee Meeeeeeee[888]
Meeee 88 Meeeeeeee-Meeeeeeee Meeeeeeee
Me8 | M | Meeeeee | Meeeeeee Meee (°M) | Meeeeeee Meee (e) | Meeee (%) ee Me8MM8 | Meeee (%) ee (Me8)8MM | Mee |
---|---|---|---|---|---|---|---|
8-MeM8M8 | Me | Me | 88 | 88 | 88 | 8 | [888] |
8-MeM8M8 | Me | M | 88 | 8 | 88 | 8 | [888] |
8-MeMM8M8 | Me | M | 88 | 8 | 88 | 88 | [888] |
M-eeeeeeee | Me | M | 88 | 8.8 | 88 | – | [888] |
8-MeM8M8 | MMe | M | 88 | 8 | 88 | – | [888] |
8-MMM8M8 | MMe | M | 88 | 8.8 | 88 | 8 | [888] |
M-eeeeeeee | MMe | M | 88 | 8 | 88 | – | [888] |
e Meeeee M: Meeeeeeee eeee eeeeeee eee ee eee eeeeeeee ee 8.8 eee% [Me8(eee)8], 8–88 eee% eeeeee, 8 eeeee ee Me–M eeeeeee, eee 8.8 eeeee ee MeMe-Me ee eeeeeee. Meeeee M: Mee eeeeeeeee ee eeeeeee eee eeeee eeeeeeee ee e eeeeeee eeee ee [Me8(eee)8] (8.8 eee%), eeee (8 eee%), MeMe-Me (8.8 eeeee), eee Me–M eeeeeee (8.8 eeeee) eeee 8 e.
e (M)-MMMMM eee eeee ee eee eeeeee.
Me eeee, eee eeeeeeeeeeee ee eeeeeeee ee eee eeeeeeee–eeeeeeee eeeeeee eeeee ee e eeeee ee eeeee eee-eeeeee eeeeeeee eeeeeeeee. Mee eeeeeeee ee [{Me[MeM(MMMM)8]8}8(μ-η8:η8-M8)] eeee M8 ee M8 eeeee eeeee eeee eeee ee M8 (Meeeee 888). Meee, eee eeeeeeee–eeeeeeeeee eeeeeee eee ee eeeeeeeeee ee e eeeeee ee eeeeeeee(MM) eeeeeeeee.[888,888]
Meeeee 888 Meeeeeeeeee ee Meeee Mee-Meeeee Meeeeeee Meeeeeeee ee Meeeeeeeeeee ee Meeeeeeeee ee Meeeeeee–Meeeeeeeee Meeeeeeee[888,888]
Meeeeeeeeeee Meeeeeeee
8-Meeee-8-eeeeee-8,8-eeeeeeeeeeeeeeeee (888):[888]
M eeeeeeeeee ee Me (88.8 ee, 88 eeee), MeMe8 (8.88 eM, 8.8 eeee), eee MMMMe (8.88 eM, 88 eeee) ee MMM (8.8 eM) eee eeeeeee eeeee eee eee 88 e. Meee eeee eee eeeee ee e eeee ee eeeeeeeeeee-8,8,8-eeeeee (888.8 ee, 8.8 eeee) eee MeM (888.8 ee, 8.8 eeee) ee MMM (8 eM) ee 8°M, eee eee eeee eee eeeeeeee eee 88 e. Mee. ee MeMMM8 eee eeeee ee 8°M, eee eee eeeee eeee eee eeeeeee eeeee ee eeeeee eeeeeeeee. Mee eeeeeee eeeee eee eeeeeeeee eeee eeee MeMMe. Mee eeeeeee eeeee eee eeeeee eeee eeeee, eeeee (Me8MM8), eee eeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee eeeeeeeeee 8% ee Me8M) ee eeee 888 ee e eeeeeeeee eee; eeeee: 88 ee (88%). MM (eeee) νeee: 8888, 8888 ee−8; 8M MMM (MMMe8, δ): 8.88 (e, M = 8.8 Me, 8M), 8.88–8.88 (e, 8M), 8.88–8.88 (e, 8M), 8.88–8.88 (e, 8M), 8.88 (e, M = 8.8 Me, 8M), 8.88 (e, M = 8.8 Me, 8M), 8.88 (e, M = 8.8 Me, 8M), 8.88 (e, M = 8.8 Me, 8M), 8.88 (e, M = 8.8 Me, 8M), 8.88 (e, M = 8.8 Me, 8M). 88M MMM (MMMe8, δ): 88.88, 88.88, 88.88, 88.88, 88.88, 88.88, 88.88, 888.88, 888.88, 888.88, 888.88, 888.88, 888.88. MM-MM e/e: 888 (M+), 888, 888, 888, 888, 88, 88.
References
[242] | Meeeee, M.; Meeeeeee-Meeeeeeeeeeee, M.; Meeee, M., M. Meeeeeeee. Meee., (8888) 888, 888. |
[827] | Meeeee, M. M.; Meee, M. M., Meee. Meee. Meee MMMM, (8888) 888, 8888. |
[828] | Meeeee, M. M.; Meeeeeeeeee, M. M.; Meeeeeeee, M. M.; Meee, M. M., M. Meee. Mee., Meee. Meeeee., (8888), 8888. |
[829] | Meeee, M.; Meeeee, M., Meee. Mee., (8888) 88, 8888. |
[830] | eee Meeeeee, M. M.; Meeeee, M.; Meeeeeeee, M.; Meeeee, M.; Meeeeee, M., M. Me. Meee. Mee., (8888) 88, 8888. |
[831] | Meeeeeee, M.; Meeeee, M.; Meeee, M., Meee. Meeeee., (8888), 888. |
[832] | Meeeeeee, M.; Me, M.; Meeeee, M.; Meeeeeeee, M.; Meeee, M.; Meee, M., Meee. Meee. Mee. Mee., (8888) 88, 8888. |
[833] | Meeeeeeee, M.; Meeeeeeeee, M.; Meeeeee, M.; Meeeeeeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[834] | Meee, M.; Meeeee, M.; Meeeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[835] | Meee, M.; Meee, M.; Meeeee, M.; Meee, M.; Meee, M.; Meeeeee, M., Meeee. Meee., (8888) 888, 888; Meeee. Meee. Mee. Me., (8888) 88, 888. |
[836] | Meee, M.; Meee, M.; Meee, M., M. Mee. Meee., (8888) 88, 8888. |
[837] | Meeeee, M.; Meeeeeee, M.; Meee, M.; Meee, M.; Meeeeeeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[838] | Meee, M.; Meee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[839] | Meeeeeee, M. M.; Meeeee, M., M. Me. Meee. Mee., (8888) 888, 888. |
[840] | Meeeeeee, M. M.; Meeeee, M., Meeeeeeeeeeeeee, (8888) 88, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 88/8, 888.